An approach to the synthesis of polyoxometalate encapsulating different kinds of oxoanions as heteroions: bisphosphitopyrophosphatotriacontamolybdate [(HPO3)2(P2O7)Mo30O90]8-.
A yellow [(HPO(3))(2)(P(2)O(7))Mo(30)O(90)](8-) anion was prepared as a tetrapropylammonium (Pr(4)N(+)) salt from a 50 mM Mo(VI)-2 mM P(2)O(7)(4-)-4 mM HPO(3)(2-)-0.95 M HCl-60% (v/v) CH(3)CN system at ambient temperature. The (Pr(4)N)(8)[(HPO(3))(2)(P(2)O(7))Mo(30)O(90)] salt crystallized in the orthorhombic space group P(nma) (No. 62), with a = 30.827(2) A, b = 22.8060(15) A, c = 30.928(2) A, V = 21743(3) A(3), and Z = 4. The structure contained a (P(2)O(7))Mo(12)O(42) fragment derived from the removal of each corner-shared Mo(3)O(13) unit in a polar position from a [(P(2)O(7))Mo(18)O(54)](4-) structure, and each side of the (P(2)O(7))Mo(12)O(42) fragment was capped by a B-type (HPO(3))Mo(9)O(24) unit. The [(HPO(3))(2)(P(2)O(7))Mo(30)O(90)](8-) anion was characterized by voltammetry and IR, UV-vis, and (31)P NMR spectroscopy. Unlike the Keggin and Dawson anions and the parent [(P(2)O(7))Mo(18)O(54)](4-) anion, the [(HPO(3))(2)(P(2)O(7))Mo(30)O(90)](8-) anion exhibited two-electron redox waves in CH(3)CN with and without acid.
Maeda
Sayuri
S
Department of Chemistry, Graduate School of Science, Kobe University, Kobe.
Goto
Takuya
T
Takamoto
Masayo
M
Eda
Kazuo
K
Himeno
Sadayuki
S
Takahashi
Hiroki
H
Hori
Toshitaka
T
D018360:Crystallography, X-Ray; D004563:Electrochemistry; D009682:Magnetic Resonance Spectroscopy; D008982:Molybdenum / Q000737:chemistry; D010087:Oxides / Q000138:chemical synthesis* / Q000737:chemistry; D013056:Spectrophotometry, Ultraviolet; D017973:Tungsten Compounds / Q000737:chemistry*
D010087:Oxides; D017973:Tungsten Compounds; C539578:bisphosphitopyrophosphatotricontamolybdate; D008982:Molybdenum